Process for the preparation of a mixture of oxygen and ammonia gases



pril 28,1936 E. w. HARVEY 2,038,562

PROCESS FOR THE PREPARATION OF A MIXTURE OF OXYGEN AND AMMONIA GASES Filed June 2l, 1953 2 ShetS-Sheec l Amm anl'a Gas ATTORNEY April 2s, 1936. E. w. HARVEY 2,038,562v PROCESS FOR THE PREPARATON OF A MIXTURE OF OXYGEN AND AMMONIA GASES Filed June 2l, 1953 2 Sheets-Sheet 2 Wa fer #ly/7 Pressure ow Pressure Sarage MOM Patented pr. 28, 1936 NITED STATES PATENT OFFICE 2,038,562 Y Pricelessy Foa THE PREPARATION' oF A MIIXTURE OF OXYGEN A'ND GASES AllIlYIONIA Application June 21, 1933,y Serial No. 676,786

1 Claim. (Cl. ,Z3-193) y This invention relates to a method for the transportation of ammonia and of solid materials soluble in ammoniacal liquids, and for the recovery of ammonia fromY solutions containing it, together with other ingredients. The invention further relates to apparatus for the treatment of ammoniacal solutions for therecovery of ammonia therefrom.

It has heretofore been known that' numerous it? solid substances, such as urea, sodium nitrate, ammonium nitratey and the like, are soluble in liquid anhydrous ammonia and in aqua ammonia. It has also been heretofore proposed toA utilize the solubility of such substances in ami moniacalY liquids for the purpose of carrying out chemical reactions between two or` more materials, particularly double decomposition reactions, between salts. A It is an object of this invention to provide an 2G economical method for the transportation of' ammonia and of solid materials soluble in` ammcniacal liquids, i; e., in liquid anhydrous ammonia or in aqueous solutions of ammonia, parr ticularly aqueous solutions containing relatively L high concentrations of ammonia, and to store such materials underconditions particularlyr advantageous with respect to the vapor pressure of the stored materials; It is a further object of n this invention to provide a method for the transportation of ammonia and solid materials in the form of a solutionl of' the solid in an ammoniacal liquid and to recover from' such solutions ammonia for use separatelyr from the other constituents of the solution. Another object of the invention is to provide a process and apparatus for the storage and treatment of ammoniacal solutions whereby ammonia may be recovered from an ammoniacal solution of a solid substance and the recovered ammonia stored either separately from the other constituents oi the solution or directly utilized, for example, by mixing it with an oxygen gas to form a gaseous mixture suitable for catalytic treatment to oxdize the ammonia. Further objects of the invention will be obvious orV will appear hereinafter.

In employing the process of this invention for the transportation and storage of ammonia and liquid, a solution of the material in an ammoniacal liquid is prepared and transported. After transportation the solution is treated to Vaporize a desired proportion of its ammonia content 55 and the resulting residue may then be stored a solid material which is soluble in ammoniacal While the ammonia which wasv vap'orized may' be mixed with an oxygen gas and the mixture catalytically treated for the oxidation of ammonia, or the vaporized ammonia may be condensed to form a liquid or, without condensation, may be absorbed inwater and the ammoniacai liquid as prepared by either of these methods may be stored or utilized directly as may be desired.

The accompanying drawings are illustrative of various types of apparatus suitable for use in carrying out the processes of this invention. In the drawings Figs. 1v tio-5 illustrate diagrammatically various modifications of the apparatus of this invention, and examples of the process of the invention will be described in conjunction with a` description of the several apparatuses shown.

With reference toFig. 1-, the numeral I indicates a storage vesselcapable of withstanding pressures above atmospheric and provided with a heating unit 2` for heating a liquid in vessel l by means of steamr introduced through pipe 3 and passing through the space between pipe 3 and an outer pipe 45.

A solution of sodium nitrate in an ammoniacal liquid may be preparedl for transportation, as for example by dissolving solid sodium nitrate in anhydrous liquid ammonia or in aqua ammonia, of relatively highv concentration, for example, an aqua ammonia containingl about equal proportions of water and ammonia. Such liquid anhydrous ammonia or concentrated aqua ammonia at ordinary temperatures has vapor pressures materially in excess of atmospheric pressure. By dissolving the sodium nitrate in the ammoniacal liquid the vapor pressure of the liquid may be substantially reduced thereby facilitating its transportation' in sealed containers of suiicient strength to withstand the reduced vapor pressures of the solution; The use of an ammoniacal solution of sodium' nitrate for transportation of the ingredients of the solution is also advantageous since such solutions occupy a smaller volume than ldo the several constituents ofy the solution, and this characteristic of the solutions makes their use forv the transportation of the ingredients of the solution advantageous.

After transportation' the ammoniacal solution of sodium nitrater is introduced into storage vessel l through a pipe 5. Ammonia gas is vaporized from the solution in tank I and is withdrawn through a pipe 6' and compressor 1 and passed to a cooling coil 8 where the vaporized ammonia iscooled to condense it as a liquid condensate which is passed through a pipe 9 into a storage vessel Ill. The vaporization of arnmonia from the solution introduced into tank I may be facilitated by heating the solution by means of heating unit 2. The condensate formed in cooling coil 8 may be a substantially anhydrous liquid ammonia which, if desired, may be stored as such in vessel I0, or the liquid ammonia. condensate may be mixed with water in a desired proportion to form an aqueous ammoniacal solution which may then be stored in tank IIJ until such time as it may be desired for use.

If desired, substantially all of the ammonia content in the solution introduced into tank I may be vaporized and transferred to tank III for storage and, if the ammoniacal solution introduced into tank I contains water, the residual salt solution thus obtained may be evaporated to dryness and the solid salt recovered for use, or the aqueous solution of the salt which, if desired, may contain a portion of the ammonia originally in the solution introduced into tank I, may be withdrawn from this tank and used in the preparation .of fertilizers as, for example, by adding the ammoniacal solution to acidic fertilizer material such as a superphosphate.

The apparatus shown in Fig. 2 is similar to that of Fig. 1 except that it comprises a stripping tower II and storage tank I2 not present in the apparatus of Fig. 1.

In utilizing the apparatus of Fig. 2 for the treatment of an ammoniacal solution of sodium nitrate, the solution is introduced into a tank I3 through a pipe Id and is withdrawn in desired proportion from tank I3 through a pipe I5 and introduced into the top of stripping tower II. Stripping tower II may contain a packing material I and be provided with heating coils Il. The solution in passing downwardly through tower Il is intimately contacted with a mixture of gaseous ammonia and water vapor, which may be evolved by heating solution in the bottom of tower II, and absorbs water Vapor from this vapor mixture. The unabsorbed ammonia passes out of the top of tower I I through a pipe I8 leading to a compressor I9 and cooling coils 20 where the ammonia is condensed and the condensate passed into a storage tank 2l where it is stored either as a substantially anhydrous liquid ammonia condensed in cooling coil 2E! or is mixed with water and the resulting aqueous ammonia stored in tank 2I. The solution in the bottom of tower II from which a. desired proportion or all of the ammonia has been removed flows out of the tower through a pipe 22 to a storage vessel I2 where the salt solution is stored until desired for use; The rate of now of solution from pipe I5 and the rate of heating by coil I'I may be so controlled as to produce a desired degree of separation or fractionation of water and ammonia.

The apparatus shown in Fig. 3 comprises a storage vessel 23 into which a solution of a solid substance in an ammoniacal liquid may be introduced through a pipe 24 and from which the solution may be passed through a pipe 25 in amounts regulated by a ow regulator 26 into the top of a stripping tower 21 which, like the stripping tower of the apparatus of Fig. 2, is provided with packing and heating coils. Air or air enriched with oxygen is introduced into the bottom of stripping tower 21 through an inlet pipe 28 and in passing upwardly through the tower in direct contact and in countercurrent flow with the ammoniacal solution descending through the tower vaporizes from the solution ammonia gas which forms with the air a mixture of gases containing ammonia and oxygen which is withdrawn from the top of the tower through an outlet pipe 29. By suitable regulation of the degree of heating of the liquid and air by means of the heating coils in the bottom of tower 21 and of the proportions of air and solution passed in contact with each other in the tower, the proportion of the ammonia in the solution which is vaporized and ratio of ammonia to oxygen in the resulting mixture of gases may be controlled. Water may also be introduced into the top of tower 21, through a pipe 3D and thus mixed with the ammoniacal solution at a point near to that at which the solution first comes into contact with the air passed through the tower.

By controlling the proportions of water and ammoniacal solution introduced into the tower the degree of removal of ammonia from the solution may be varied independently of the control of the degree of ammonia removal by means of the heating of the solution in the bottom of the tower and the proportions of air and solution contacted with each other. This introduction of the water also provides a means for adding av desired proportion of water to the sodium nitrate solution, for example, which leaves the bottom of tower 21 and passes through a pipe 3I into a storage tank 32. The solution in storage tank 32 may be used for fertilizer manufacture or, if desired, by completely removing the ammonia from the solution introduced into tower 2l, the sodium nitrate may be recovered as the solid from the solution leaving the tower. In such a case it is desirable to introduce little or no water into the solution being treated in tower 21.

The apparatus shown in Fig. 4 comprises a storage vessel 33 into which an ammoniacal solution .of urea, for example, containing a relatively high proportion of ammonia may be introduced and from which the solution may be withdrawn through a pipe 34 and ilow regulator 35 and introduced into the top of a stripping tower 36. The operation of stripping tower 36 is similar to the operation of tower 21 as described in conjunction with the apparatus shown in Fig. 3. Thus the ammoniacal-urea solution flows downwardly through tower 36 in countercurrent low with air introduced into the tower from a pipe 37, the air and solution being heated in the bottom of the tower by means of heating coils 38. Water may be introduced into the top of tower 36 from a pipe 39 and the mixture of air and ammonia withdrawn from the tower through a pipe for catalytic treatment to oxidize the ammonia by means of the oxygen contained in the mixture of gases. The residue from which ammonia has been removed is withdrawn from tower 36 through a pipe 4I and pump 42 and passed to a storage Vessel 43 where it is stored and from which it may be withdrawn through a pipe 45 and pump 46 for use.

In treating a urea-ammonia solution, particularly one which also contains carbon dioxide in the form of ammonium carbamate or carbonates, the introduction of water from pipe39 and the countercurrent ow of the solution and air into which ammonia is vaporized serves to retain the carbon dioxide in the solution while removing the ammonia present in excess of the amount equivalent to that which combines with the carbon dioxide tol form ammonium carbamate or carbonates. Thus, the apparatus shown in Fig. 4': isl particularly suitable for the treatment of a solution containing, for example:

Sucha. solution may be stripped of all or any de sired proportion of its free ammonia in tower 36 with theV production of a mixture of air and ammonia. suitable for catalysis to oxidize the ammoniawhile asolution containing urea, ammonium carbamate and Water is withdrawn to tank 43.. This sol'ution may be utilized in the productionr of mixed fertilizers as, for example, by its addition to superphosphate or it may be concentrated. and solid urea recovered from the solution.

The apparatus of Fig. 4 also includes a pipe 44 whereby theV concentrated ammoniacal solution from tank 33 may be withdrawn in any desired proportions for use directly in the production of mixed fertilizers by addition, for example, to superphosphate or mixtures containing the same. The apparatusv also comprises a pipe 41 communicating between pipe 45 and tank 33, whereby solution from tank 43 may be passed into tankV 33 to dilute the solution in tank 83 with respect to its ammonia content or, if desired, solution from tank 33 may be introduced into solutionv being withdrawn, from tank 43 through pipe 55 to increase the ammonia content of the latter solution to a desired degree, particularly when this solution. is to be added to superphosphate.

The apparatus shown in Fig. 5 comprises a storage tank48 into which a solution of sodium nitrate in. anhydrous liquid ammonia may be introduced. Ammonia gas may be withdrawn from the solution in tank 48, passed through a pipe 49 and introduced into water in tank 55, where the ammonia is absorbed to form aqua ammonia. The solution in tank 48 may be heated, if desired, and the aqua ammonia in tank 56 may be cooled so that a desired proportion of the ammonia in the solution in tank 48 may pass into and be absorbedr by the water in tank 58. The aqua ammonia from tank 56 may be forced by means of a pump 5| throughapipe 52into a tank 53 provided withY an overflow return 54 leading back to storage tank 50. A by-pass pipe 55 about pump 5| is provided so that, if desired, by having valves 56, 51, 58, and 59 closed and by opening Valve 66 in a vent from tank 53, aqua ammonia may be transferred from storage tank 50 into tank 53 by increasing the pressure upon the aqua ammonia in tank 50. From tank 53 the aqua ammonia is withdrawn through a pipe 6| and flow regulator 62 into a stripping tower 36 like tower 36 of Fig. 4, wherein the aqua ammonia is treated with air in the manner described above for the treatment of the urea-ammonia solution in the apparatus of Fig. 4, to vaporize ammonia from the aqua ammonia with the formation of a mixture of air and ammonia suitable for catalytic treatment to oxidize the ammonia. The water leaving tower 36 through a pipe 63 may be stored and subsequently returned to tank 58 for again absorbing ammonia to form aqua ammonia suitable for treatment in stripping tower 36. If desired, a suitable proportion of the ammonia may be left in the water leaving tower 36 by regulating l the proportions of aqua ammonia introduced into the tower and air` contactedv with the:- aqua ammonia and the degree of heating of the air and liquor' in tower 36'.. The resulting relatively dilute` aqua.l ammonia maybe utilized in the production of; fertilizers as, for example, by addition to a sup'erphosphate.

The apparatus of Fig.. 5 alsoincludes a pipe 64 leadingY from; the bottom of tankf48 into tank 58 and the ammoniacal solutionV from tank 48V may be introducedinto tank 50- andv thence transferred to tank 53'. and passed into stripper 36 where it may be treated with'air to Vaporize ammonia from the solution in the manner described for the treatment of ammoniacal-urea solutions in the; stripping tower ofv Fig. 4. The ammonian air mixture thus obtained leaves tower 36 through a pipe 65"-, and the residual sodium nitrate solution containing.v more or less ammonia is withdrawn fromY the tower through pipe 63.

The apparatus of Fig. 5 also includesA a pipe 66 and flow regulator 61S through which gaseous ammonia vaporized from the solution .in tank 48 may bel directly withdrawn, mixed with the desired proportion of oxygen and passed directly to an ammonia oxidation systeml The solution in "f tank 48' containinga reduced proportion of ammonia may then be passed intotank 50 for treatment in stripper 36 to recover additional arnmonia in the manner described above, or it may be withdrawny through a pipe 68 for use in the production of fertilizers; If desired, provision maybe made for heating the solution in tank .18 to facilitate Vaporizing the desired proportion of its ammonia content before withdrawing the solution from tank 48' for use in the preparation of fertilizers. Tank 48 is also provided with a pipe 69 whereby water may be introduced into the solution in the tank.

The following example illustrates one method of treating an ammoniacal sodium nitrate solution utilizing the apparatus of Fig. 5. Such a solution containing for example Percent Sodium nitrate 26 Free ammonia 50 Water 24 and` having a vapor pressure at ordinary atmospheric temperatures of about 50 to 100 pounds per square inch. of gauge pressureis introduced into tank 48 under its own vapor pressure into water, which has previously been passed intothe tank from pipe 69, in the. proportions of about 40 tons of the ammoniacal sodium nitrate solution to 20 tons of water. About, 21/2 tons of ammonia gas is permitted. to Vaporize and flow under its own pressure through pipe 49 into tank 50 into which about 71/2 tons of water have been introduced. The ammonia is absorbed in the water to form about 10 tons of aqua ammonia containing 25% ammonia; the residual solution in tank 48 amounting to about 571/2 tons, contains about 17% tons of free ammonia, about 101/2 tons of sodium nitrate and about 291/2 tons of water. If desired, instead of introducing all of the water to be mixed with the ammoniaoal solution in tank 48 before introducing the ammoniacal solution into the tank, the water and ammoniacal solution may be simultaneously introduced into the tank. This mode of operation facilitates maintaining the desired ammonia Vapor pressure in tank 48 to force the ammonia gas into tank 50 while the arnmoniacal solution is being introduced into tank 48. The heat evolved by dilution of the relatively concentrated Cil ammoniacal solution in tank 48 also facilitates the vaporization of the ammonia from the solution. The ammoniacal solution in tank 48, which has been diluted with water and from which a portion of its original ammonia content has been vaporized, may be withdrawn from the tank and passed through pipe 68 for use in treating superphosphate. The aqua ammonia in tank 50 is passed to tank 53 and thence into stripping tower 36 where it is treated with air to recover a desired proportion of its ammonia content, and the weak aqua ammonia withdrawn from tower 35 may be returned to tank 50 for absorption of ammonia from additional quantities of ammoniacal sodium nitrate solution introduced into tank G3.

The process and apparatus of this invention include numerous features of practical importance in commercial operations. Many fertilizer plants, for example, require for the preparation of mixed fertilizers not only nitrogenous chemical fertilizer materials such as urea, sodium nitrate, ammonium nitrate, calcium nitrate, ammonium sulfate and the like, but also free ammonia and nitric acid which may be prepared by the catalytic oxidation of ammonia. There are also available at many synthesis plants both ammonia and nitrogenous chemical fertilizers. By employing the process and apparatus of this invention, the chemical fertilizers and ammonia may be conveniently shipped in the form of ammoniacal solutions of the solid substances whereby liquid compositions containing high proportions of valuable ingredients but having relatively low vapor pressures as compared with anhydrous liquid ammonia and concentrated aqua ammonia, may be shipped, thus introducing material savings in transportation costs. On the other hand, my invention provides a method and apparatus for treating these ammoniacal solutions for the recovery therefrom of desired proportions of the ammonia contained in the solution for use separate from the other ingredients, particularly for oxidation to nitrogen oxides which may be used directly or after absorption in Water to form nitric acid by the fertilizer manufacturer as, for example, for the treatment of phosphate rock to render the P205 content of the rock available as a plant food.

The following are speciiic examples of advantages derivable from this invention:

A concentrated aqueous solution of sodium nitrate and ammonia may be prepared and shipped in closed containers under its own reduced vapor pressure. The purchaser of this solution may then treat it in accordance with the process described above in conjunction with the apparatus shown in Figs. 1 and 2, for example, to convert the aqueous solution into a solution containing all of the nitrate but a smaller proportion of the ammonia, which solution will have a low Vapor pressure and thus may be stored in low pressure equipment under substantially atmospheric pressures. The vaporized ammonia may be condensed to form a concentrated or substantially anhydrous liquid ammonia which requires for its storage high pressure equipment. The capacity of the high pressure storage vessels for containing the liquid anhydrous ammonia is, however, relatively small as compared with the capacity for the storage vessels required for the original sodium nitrateammonia-water solution, and any increase in the expenses for storing the anhydrous liquid ammonia because of its higher vapor pressure than the original aqueous ammoniaca] solution is oil.- set by the decreased expense involved in storing the smaller volume of residual ammonia-sodium nitrate-water solution having a vapor pressure of about atmospheric after removal of a portion of the ammonia.

Again, when instead of removing a portion of the ammonia and storing it in the form of substantially anhydrous liquid ammonia, the vaporized ammonia is transformed into aqua ammonia in the manner described above for the process as carried out in the apparatus of Figs. 1 and 2, for example, the invention is of advantage since both the residual sodium nitrate-water solution and the aqua annnonia containing a portion of the ammonia in the original relatively concentrated solution may have vapor pressures of about atmospheric and thus do not require high pressure equipment for their storage.

Numerous other advantages will be apparent from the foregoing description of my invention.

I claim:

The process for the preparation of a mixture of gases containing oxygen and ammonia suitable for the catalytic oxidation of the ammonia which comprises passing an oxygen gas into direct contact and in countercurrent iiow with a liquid containing dissolved therein urea, carbon dioxide and free uncombined ammonia, thereby vaporizing ammonia from said liquid and producing said mixture of gases and introducing water into said liquid at a point near that at which the liquid is rst contacted with the gas to retain carbon dioxide in the liquid while removing free uncombined ammonia present therein.

EDWARD W. HARVEY. 

